Water insoluble ortho-disazo dyestuffs and fiber dyed therewith



Patented Jan. 18, 1938 UNITED STATES PATENT OFFICE WATER INSOLUBLE ORTHO-DISAZO DYE- STUFFS AND FIBER mmormmnwrrn Delaware No Drawing. Application January 27, 1934, Se-

rial No. 708,691. In Germany February 2,

8 Claims.

The present invention relates to Water-insoluble ortho-disazo dyestufis and to fiber dyed therewith; more particularly it relates to dyestuffs having the following general formula:

wherein R1 stands for a naphthalene, anthracene, carbazole or benzocarbazole radical, R2 means a radical of the benzene or naphthalene series and wherein the nuclei signified by I and II are substituted by methyl, halogen, alkoxy, phenoxy, nitro, trifiuoromethyl, alkylsulfonyl, arylsulfonyl, sulfonic acid-dialkyl-amino, N-methyl-ethanesulfamino or carboxylic acid-alkyl-ester groups.

We have found that valuable water-insoluble orthodisazo dyestuffs are obtainable by diazotizing substitution products of 2-amino-1,1'-azobenzene and coupling them with hydroxy-arylcarboxylic acid arylides, such as arylides of 2,3- hydroxynaphthoic acid, of 2,3-hydroxyanthracene carboxylic acid, of ortho-hydroxycarbazole carboxylic acids, of ortho-hydroxybenzocarbazole carboxylic acids, or with compounds containing' a reactive methylene group capable of coupling with diazo compounds, such as pyrazolone derivatives or arylides or esters of betaketo-carboxylic acids, among which arylides of diacetic acid and other acylacetic acids, or diacylacetyl arylamines, such as diacetoacetylbenzidine or-tolidine, may be mentioned. The components wherein R and R1 represent substituted benzene I radicals and R2 means the radical of an hydroxy- 'aryl-carboxylic acid arylide, of a p-keto-carboxarylide or of a pyrazolone derivative.

The smooth course of the diazotization and the coupling must be regarded as highly surprising. (Cf. Kiinstliche organische Farbstofie of Fierz David, 1926, III vol., page 106). In this manacetoacetic acid, benzoylacetic acid, terephthaloyb -ylic acid ester and of a B-keto-carboxylic acid ner it is possible to prepare dyestuffs which may be used for the same purposes as the azo dyestuffs hitherto known. The dyestuffs may be prepared either in substance, on the fiber or on any of the usual substrata adapted for the production of lakes. 1

In comparison with the para-disazodyestuffs which may be obtained according to U. S. Patent No. 1,871,947 by coupling diazotized paraamino'- azo compounds of the benzene series with 2,3- hydroxynaphthoic acid arylides, the ortho-disazo dyestuffs of the present invention are distinguished by an essentially better fastness to boiling lye (boiling for 6 hours at atmospheric pressure with cc. of caustic soda solution of 40 B. in 10,000 cc. of water per 1000 grams of material) 1 The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight, unless stated otherwise:

(1) Cotton fiber is padded in the usual manner with the following grounding liquor: 12 parts of 1- (2 ,3'-hydroXy-naphthoylamino) -2-methyll-chlorobenzene, 36 parts by volume of caustic L dium nitrite are dissolved in water and added,

thereto. When the diazotization is finished, the whole is made up with water to 800 parts by volume and rendered neutral by means of sodium acetate. After washing and soaping at the boil, the dyeing represents a Bordeaux-red:

tint having a very good fastness to washing and to chlorine.

The dyestuff corresponds to the following for- (2) Cotton fiber is grounded as stated in Example 1 with 5 parts of 2,3-hydroxynaphthoylaminobenzene, 7.5 parts by volume of caustic soda solution of 30 B., 10 parts by volume of Turkey red oil of 50% strength and 5 parts by volume of formaldehyde of 33% strength. The dyeing is developed with the following diazo solution:

3.1 parts of 5-methyl-4-methoxy-2amino-2,4'--

dichloroazobenzene are diazotized as described in Example 1 and the diazo solution is rendered neutral. The dyeing is washedand soaped at the boil and represents a red-brown tint of very good fastness to washing and to chlorine.

The dyestuif correspondsto the following formula:

I O1 IIII N ON: 0 CH:

C] II OHr-C 0-4111-0 ONH (4) The diazo solution mentioned in Example 3 'y1-3-methyl-5-pyrazolone.

is coupled with 1.8 parts of finely divided l-phen- The dyestufi is filtered by suction and washed out; it formsa red powder and possesses the following formula:

(5) Cotton fiber, is grounded as described in Example 2. The dyeing is developed with the following diazo solution: 3.2 parts of 5-methyl- 4- methoxy -2- amino -2- chloro-4'-nitroazobenzene are diazotized as described in Example 1 and the diazo solution obtained is neutralized. The dyeing which has been washed and soaped at the boil represents a deep brown shade of very good fastness to washing and to chlorine, and of very good dischargeability. The dyestuff corresponds to the following formula:

OCH:

By using, instead of 2,3-hydroxynaphthoylaminobenzene, 1 2, 3'- hydroxynaphthoylamino) -2-methylbenzene for the grounding liquor, a dark olive-brown dyeing is obtained; by using 1 -(2', 3- hydroxynaphthoylamino) -4- methoxybenzene there is obtained a deep ye1l0wish-brown. Both dyeings possess a very good fastness to washing and to chlorine, and a very good dischargeability.

The following table indicates a further number of other ortho-disazo-dyestufis, obtainable according to the present invention:

Coupled with the following Diazo compound from: arylide of 2,3 hydroxy- Shade naphthoic acid:

1 5meth l--methoxy-Z-aminm4'-chloro- Anilide Red-brown.

azobenzene 2 S-methyH-methoxy-2amino-2-methoxydo Y el 1 o w i s h azobenzene V brown. 3 5-methyl-4-methoxy-2-.amino-4-methoxydo Do. 30 azobenzene 4 5-methyl-4-methoxy-2-amino- 2,4 di- Reddish brown.

methylazobenzene 5 5-methyl-4-methoxy-2 amino-3-nitro-4- Y e l l o w i s h methoxyazobenzene brown. 6 fi-methyl-i-methoxy-Mmino-W-methoxy- Deep brown.

fif-nitroazobenzene 7 5-methyl-4-methoxy-2-amino-4'-nitroazo- Y e l l o w i s h.

. benzene brown.

8 5-methyl-4-methoxy-2amino-2,6'-di- Deep reddish ch1oro-4-hitroazohenzene brown. 9 5-methyl-4'methoxy-Z-amino-Y-methoxy- Do.

4-nitroazobenzene l0 5-methyl-4-met hoxy-24amino-2',5-di- Y e 1 l o w i s h methoxy-y-mtroazobenzene wn. T0 11 5 methyl 4 methoxy 2 amino 2- Deep reddish methyl-4-nitroazobenzene. brown. 12 5 methyl 4 methoxy 2 amino 3- Very yellowish methyl-4-nitroazobenzene. brown.

13 5-methyl-4-methoxy-2-amino-2-4- Deep olivedinitroazobenzene. brown. 14 5- methyl 4 ethoxy 2 amino 2- Deep brown. 7 ch19:o-4'-nitroaqobenzene.

5 15 4, 5-dunethyl-2-anuno 4-mtroazobenzene. .....do Red-brown.

, g o Coupled with the following Diazo compound from: erylide oi a-hydmxy- Shade naphthoic ac d:

97 t-llritro-emethoxy-zamino-2-chloroazoiParo-anisididenn Brown-rod. enzene. 98 5-methyl4-methoxy-2-amino-2,4-dibro- Anilide Red-brown. i moazobenzene. v 99 5-methy1-4-methoxy-2-omino-2-ethoxy Ortho-anisidide Yellowlsh brown 4'-nitro-5-methylazobenzone. 100 5-methyl-4-methoxy-2-amino-iGphenoxy- Anilide Do.

azobenzene. 101 4,5-dunethyl-Z-am1no-2-chlcro-4-mtro- -...do Black-brown;

azobenzene. i V 102 5-methyl-4-methoxy-2-amino-4-N- Ortho-amsidido Red-brown. I

methyl-ethanesuliamide-ezobenzsno. I 103 5-methyl-4-methoxy-2-amino-2 oarbor' Anilide Brown-red.

ylic acid-methyl-ester-azdbenzene. I 104 5-methyl-4?methoxy-2-amino-2'-phonyldo Brown. sulfonyI-4-nitroazobenzene.

Diazo compound from Coupled with Shade I 105 5-methyl-4-methoxy-2-amino 2ehloro-yl-(3-hydroxy-7.,8-bonzocar- Blue-gray.

nitroezcbenzene. hazole-2-carbonylamino)- a I z-mothyl-i-mothoxyben' zone. 106 5-methyl-4-methoxy-2-amino-2-methyi- 1-(3'-hydroxy-7,8'-benm- Khaki-olive. i

5-chloroazobenzene. carbozolo-2-carbonylamino)-2-methyl-4-methoxy- I benzene. 107 5-methyl-4-methoxy-2-amino12- 1-(2'-hydroxycarbazola-3'- Yellow-brown.

methoxy-5-nitroazobenzene. gzrbonylaminm-i-chlotoj l mane. 108 E-methyl-4-methoxy-2-amino-2-nitro-4- 1-(2-hydroxyanthraosne-3'- Olive.

methoxy-azobenzene. carbonylamino)-2-methyl- I benzene. 109 4,5-dimethoxy-2-amino-2'-chloro4-nitro- .do Black-groom; azobenzene. I 110 5-methy1-4-methoxy-2-amin0-2#ch1or0' ...-.do Olivmgraen.

4methylazobenzene. g i so 111 5-methyl-4-methoxy-2-ammo-2-mtro-4'- l-(3-hydroxy-7,8-benzo- Mole-brown;

chloroazobenzone. .carbazole-2 -carbonylam- I ino)+methoxybenzene.

Since, an object of the present invention is to provide dyestufis of good fastness properties which dyestuffs are insoluble in water and alkali'es, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render organic compounds 0 soluble'in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. Substituents of'this' kind are, for instance, the sulfonic acid and the carboxylic acid group.

We claim: 1. The water-insoluble ortho-disazo dyestufi of the following formula: 0 l 1 Cl CH:

OQNON=N com I of the following general formula:

o I 01 CH:

O|N- N=N 0 CH:

yielding,- when produced on the fiber, a dark olive-brown dyeing of very good fastness to washing andto' chlorine and of very good dischargeability.

4. The water-insoluble ortho-disazo dyestuffs I I x yielding, when produced on the fiber; a deep brown dyeing of. very good fastness to washin Y and to chlorine and of very good discharges60 ability. I N 2. The water-insoluble ortho-disazo dyestuft u of the following formula: I l N I OH 7 I X01 CHI K V MON: 0GB. I I

, I v \C0-NH--R:

E wherein R: means a member of the group conl I sisting'of radicals of the benzene and naphthalene 70 series, B: stands for a radical of the group consisting of halogen-phenyl, dihalogen-phenyl,

halogen-methyl-phenyl, nitro-phenyl, dinitrcnitrodimethyl- 7 5 phenyl, nitro-alkoxy-phenyl, nitro-dialkoxy- 5. Fiber dyed with the ortho-disazo dyestufi phenyl, nitro trifluoro-methyl-phenyl, nitroas claimed in claim 1.

arylsulfonyl phenyl and nitro-alkoxy-methyl- 6. Fiber dyed with the ortho-disazo dyestufl as phenyl, X stands for a member of the group conclaimed in claim 2.

sisting of hydrogen, alkoxy, methyl, halogen and '7. Fiber dyed with the ortho-disazo dyestuff as 5 nitro and Y for a member of the group consistclaimed in claim 3.

ing of a methyl and alkoxy, yielding, when pro- 8- Fiber dyed with the ortho-disazo dyestufis as duced on the fiber, brown dyeings of good fastness claimed in claim 4. properties, particularly of very good fastness to ERWIN HOFFA.

l0 washing and to chlorine. HANS HEYNA. 10 

